Tellurium is an essential elemental in modern science and belongs to scattered elements. At present, the extraction and recovery of tellurium is primarily achieved by collectively recovering from byproducts during nonferrous metal smelting processes, for example, recovering from anode slimes of copper and lead etc., or extracting from primary tellurium ores.
Tellurium may be incorporated into steels to increase ductility, and serve as brightener in electroplating solution, catalyst in petroleum cracking, coloring material for glass, and also may be added into lead to increase its strength and corrosion resistance. Highly pure tellurium may be used as an alloy component for thermoelectric materials; bismuth telluride is a good refrigeration material; semi-conducting compound As32Te48Si2O is a material for manufacturing storage devices of computer; ultrapure single crystal tellurium is a novel infrared material. Highly pure tellurium plays important roles although little is used. Tellurium is also one of the best primary materials for solar cell, which has the largest conversion coefficient, relatively low cost and best benefit. Cost is essential for popularization of solar energy, the eternal energy source, and it is thus critical to obtain advancement in the process technology of tellurium extraction, minimize the cost, and achieve substantially no Three Wastes, zero emission and best product quality in practical production.
There have been various reports and patents concerning extracting tellurium from tetradymites or other Te-containing raw materials with wet process, and lots of works have been done by the experts. For example, Chinese patent application No. 99111440.X entitled “Process of Extracting Fine Tellurium from Tellurium Polymetallic Ores” discloses a process of extracting tellurium with wet process, in which hydrochloric acid is used for leaching, the leach solution is reduced by sulfur dioxide gas and then precipitated to give crude tellurium powders which subsequently react with oxidants in the hydrochloric acid solution to yield an intermediate product, TeO2, and fine tellurium product is finally collected upon electrolysis. Although fine tellurium with 99.99% purity can be obtained after electrolysis employing the hydrometallurgical method disclosed by this application, the whole process has relatively high production cost, high energy consumption, low recovery rate and low yields, wherein serious environmental problems such as large amount of waste gases and waste water occurs and other byproducts are not comprehensively utilized.
In another case, Chinese patent application No. 93115389.1 entitled “A Production Process of Extracting Fine Tellurium from Primary Tellurium Ores by Wet Process” discloses a method of producing fine tellurium from primary tellurium ores, which comprises leaching tellurium and bismuth by high temperature oxidation in hydrochloric acid medium, reducing by sulfur dioxide to give crude tellurium powder, and obtaining fine tellurium through chemical purification and electrolytic purification, and further obtaining an intermediate bismuth-containing product upon hydrolysis of the neutralized bismuth-containing reduction solution. This method requires external heating to 80° C. or more, which doubtlessly increases cost, and employs an electrolysis process leading to issues such as high energy consumption. In addition, the waste solution and waste residues are not comprehensively utilized during the production process whereby serious environmental problems and resource wasting issues emerges.
In bismuth recovery from tetradymites by hydrometallurgical methods, in general, iron is added into the acidic solution after recovering tellurium for reduction, yielding primary spongy bismuth product of low purity. The spongy bismuth produced by this method has low values, high cost and poor economical benefits. It has not been reported to directly produce 99.99% Bi2O3 from tetradymites.
With regards to the Three Wastes concerning environmental protection, less waste gases and residues are produced in hydrometallurgical methods than in pyrometallurgy methods, whilst much more waste water is produced, which is a serious environmental issue for hydrometallurgy.